Process for dyeing or coloring cellulose esters and cellulose ethers



acid, cyanacetic esters,

Patented Feb. 18, 1936 UNITED. STATES PATENT OFFICE PROCESS FOR. nmnve CELLULOSE ESTERS ETHEBS Franz Ackermann,

Binningen, Switzerland, assignor to the B COLORING AND CELLULOSE near Basel, firm Society of Chemical Industry in Basle, Basel, Switzerland No Drawing. Serial No. tion April 2,

Original application May 611,758. Divided and this 1935, Serial 16, 1932, applica- 14,37 5. In

Switzerland May 23, 1931 8 Claims.

methylimidazols, acetylacetone, benzoyiacetone dihydroresorcinols, benzylcyanide, cyanacetic cyanacetophenone, rhodanines and the like are capable of reacting with cyclic compounds selected from a group consisting of aromatic aldehydes and aromatic nitroso compounds and containing reactive oxygen-atoms, with the formation of colored products. The reaction leading to such products occurs quite generally according to the following scheme:-

, wherein H2 represents the two hydrogen atoms of the methylene group capable of reaction. In the products of the above mentioned formula the double linkage, which does not belong to a quinoid system, 'playsthe part of the main chromophore.

This invention is based on the discovery that these products, which quite generally correspond to the general formula Q 7 p R1=.BR2

wherein R1 stands for any residue of a compound containing a reactive methylene group, a: for OH or N, and R2 for the residue of a compound containing the reactive oxygen atom, are very well suited for dyeing, printing or coloring cellulose esters and cellulose ethers, such as acetate silk or nitro-cellulose varnishes. The products dye these materials various shades which may be distinguished by their purity in combination with other good properties of fastness. 0

Among the numerous compounds which here come into consideration, those are particularly valuable which contain a basic group such as an NH: group or an N(alkyl)z group; Among these compounds those in turn are especially valuable in which the residue R2 above defined is the residue of an aromatic amino aldehyde. Nevertheless it will be clear from the description and from the table that useful results are obtained with practically any cyclic aldehyde, ketone or nitroso compound. p

The following examples illustrate the invention, the parts'being by weight:

Example 1 0.5 part of the condensation product from (C1. 8-5) 1- (2-ch1oro) -phenyl-3-methyl-5-pyrazolone and paradimethylaminobenzaldehyde (which may advantageously be obtained by heating the components in dilute hydrochloric acid) is brought into a fine state of sub-division, for example by dissolving it in alcohol, pouring the solution into water, filtering and triturating the residue with sulfite cellulose waste liquor or Turkey red oil, and is then introduced into about 3000 parts of water in which have been dissolved 6 parts of soap. 100 parts of acetate silk are entered at about 40 C., the temperature is raised to 75-80 C. and dyeing is continued for lg hour to 1 hour at this temperature. The material is then rinsed, brightenedand dried in the usual manner. The acetate silk is dyed vivid strongly reddish yellow shades.

If the condensation product used inthis example is used'as a yellow component in the production of mixed shades, for example grey, the dyeings obtained are not phototropic.

Example 2 0.5 part of the condensation product from cyanacetic acid ethyl ester and paradimethylaminobenzaldehyde, which has been brought into a state of fine sub-division, for example by dissolving it in alcohol, pouring into water, filtering and triturating the residue with sulfite cellulose waste liquor or Turkey red oil, is introduced into about 3000 parts of water in which 6 parts of soap have been dissolved. 100 parts of acetate silk are entered at about 40 0., the temperature is raised to 75-80" C. and dyeing is continued for to 1 hour at this temperature. The material is then rinsedQbrightened and dried in theusual manner. The acetate silk is dyed vivid pure greenish yellow shades.

Similar dyeings are obtained by using instead of cyanacetic acid ethyl ester another ester of cyanacetic acid, such as the methyl, ,isopropyl or butyl ester, and by using instead of para-dimethylaminobenzaldehyde, paradiethylamino-benzaldehyde or 2-chloro-4-dimethylaminobenzaldehyde.

Instead ofdimethylaminobenzaldehyde there may obviously be used dipropyl-, or diamylaminobenzaldehyde. Monoalkylaminobenzaldehydes may also be used.

Example 3 An acetate silk fabric is printed with a printing color containing per litre 20 grams of the condensation product from cyanacetic acid and paradimethylaminobenzaldehyde (which may be ob- 5 parts of the dyestuff from cyanacetic acid and paradimethylaminobenzaldehyde are dissolved in.3000 parts of water with the aid of 2.5 parts of anhydrous sodium carbonate. parts of acetate silk are dyed in the dye bath thus prepared for 1 hour at 40-75 C. with the addi tion of 6 parts of concentrated sulfuric acid and 10 parts of Glauber salt. The acetate S111: is dyed a beautiful pure greenish yellow.

Acetate silk may be dyed in a similar manner by using instead of the sulfuric acid 8 parts of acetic acid of 84 per cent strength.

The manner of working described in this example is also suitable ior those products whose salts are colored.

Example 5 The procedure is as described in the first paragraph of Example 1, with the exception that instead of the condensation product therein named there is used the condensation product from paranitrosodimethylaniline and 1-phenyl-3-methyl- S-pyrazolone. The acetate silk is dyed a beautiful violet bordeaux.

The following table illustrates the shades which 'can be obtained by means of some of the condensation products used in the present invention.

Color on acetate compound g z methylene Aldehyde or nitroso compound silk or in 9. nitrocellulose varnish 1 Benzyl cyanide Para-diethylaminobenzaldehyde Yellow.

2 do Para-dnnethylaminobenzaldehyde Do.

3 Para-nitrosodimethy Orange.

4 p-nitrobenzyl cyanide Para-dimethylaminobenzaldehyde Do.

5 -..do Para-nitrosodlmethylaniline Red.

. 6 Diketohydrindene Para-dimethylaminobenzaldehyde Orange.

7 do Para-nitrosodimethy Violet.

8 Nitromethane Para-dimethylaminobenzaldehyde Orange.

9 do Ortho-chloro-para dimethyl-amino-benzaldehyde. Do.

10 Molomfrde Para-dunethylammobenzaldehyde Greenish-yellow.

11 do 0rtho-chloro-para-drmethyl-amino-benzaldehyde Do.

12 do Para-nitrosodlmethy Orange.

13 Hydroxytlnonaphthene Benzaldehy Yellow.

14 do Nitrosodimethylanilinm Violet-red.

l5 do 2-chloro-4-din ethylaminql-nitrosobenwne Violet.

l6 do 2-hydroxy+dimethylam1no-1-nlh'osobenzene Do.

17 do Para-mtrobenzaldehy Yellow.

18 Ortho-chlorobenzaldehyde Do. do Para-nitrobenzaldehy Do. d Furl'ur Do.

fi-ammo-hydroxythionaphthene Benzaldehyde Orange.

5-methylhydroxyth1onaphthene. Para-nitrosodimethy Red-violet.

5-chloro-7-methyl-hydroxythmnaphthene. Violet.

Dimethylammobenzalaeetone. Para-dimethylaminobenzaldehyde Orange. do Ortho-chlorobenzaldehyde- Do. do Para-mtro-benzaldehyde.- do Cinnamaldehyde Red-orange do Para-llltl'osodlethylnnilinn range.

Cyanacetic acid ethyl ester Terephthalaldehydo Yellow.

do Para-dimethylaminobenzaldehyde (alter condensation with amm 0- ma. 31 do Para-dimethylaminobenzaldehyde (after condensation w'ith ethan- Do.

olamme 32 do Para-dimethlaminobenzaldehyde (after condensation with diethyl- Orange.

armn

33 do Paradimethylaminobenzaldehyde (alter condensation with mono- Yellow.

ethylamme).

34 Gy acid ooilido Para-dimethylaminobenzaldehyde Do.

35 Oyanacenc acid monohydrmidn [in Do.

36 Oyanaeetc acid-parado Do.

37 Cyanacetc acid ethyl ester Product of coupling diazotized para-aminobenzaldehyde'and dimeth- Red.

ylamhne.

38 1-phenyl-3-methyl-&pyrazolone o D0.

39 .i do 2 y Orange.

4O 1-phenyl-3-methyl-5-pyrazolone ortho-chlorobenzaldehy Do.

41 do Piperonal. Do.

42 do Cinnamaldehy Do.

43 do Para-aminobenzaldehy Do.

44 3-methyl-5-pyrazolone Para-dimethylaminobenzaldehyde Do.

45 1- (meta-amino)- phenylw'i-methyl-dpyrazodo Do.

46 l-(lpara-chloro) -phenyl-3-methyl-5-pyraw Para-diethylaminobenmldehyde Do.

one.

47 l-(meltg-arlliiinogd-phenyl-6-pyrazolone-3- Para-dimethylaminobenzaldehyde. Yellow-red.

car xy cac 48 l-iortho-chloro)phenyl-3-methyl-5-pyrazo- Ptodltlfit oi eoupling diazotized para-aminobenzaldehyde and di- D0.

one. me y e.

49 do Product of coupling diazotized pare-aminobenzaldehyde and Orange.

aniline.

50 l-phenyl-o-pyrazolonwcarboxylic acid Benzaldehyde Do.

ethyl ester.

51 do Para-dimethylaminobenzaldehyde Yellow-red.

52 l-hydroxynaphthalene. do Do.

53 A mlxvnhpnnrm (in Yellow.

54 Methoxyaeetcphenone. do Greenish-yellow.

65 nhnnnnn dn Golden-yellow.

56 2Z4-dikBtOt6Cmhymnthin1nla (In Greenish-yellow.

57 N-ethylrhodanine 2:4-diaminobenzaldehyde-.- Orange.

58 Rhodnnim B-indolaldehyde Yellow.

59 Barbituric acid Para-dlmethylaminobenzaldehyde Rose.

60 Ethyl molooom do Yellow.

61 Ethyl aeetoaoetatedo Do.

62 Aeetoaeetam'lide do Do.

63 Aeetoa'eetic aeid-ortho-anisi do Do.

64 Acgtoacetic acid-para-dimethylaminoanildo Do.

Color on acetate Compound g macaw methylene Aldehyde or nitroso compound silk or in a nitrop cellulose varnish 2:4-dioxyquinoline Para-dimethylaminobenzaldehyde. Yellow. 66 Desoxybenzoin; Nitrosodiethylaniline Do. 67 6 (2 1di1lntro) phenylaminomethylbenzi- Pare-dimethylaminobenzaldehyde. Do.

1m am e. 68 Do. 69 Do. 70 Bright blue-red. 71 Orange. 72 Violet. 73 Orange. 74 2:5dimethylpyrazine Yellow. 75 Red-yellow. 76 F Yellow. 77 para-xylylene-dicyanide o Do. 78 Indo Nitrosobenzene Red. 79 -do Para-hydroxynitrosobenzene. Brown. 80 2:3-naphthio-indox l. Nitrosodimethylaniline Violet. 81 Oyenacetic acid at yl Para-aminobenzaldehyde Yellow. 82 do 3-nitro4-dimethylaminobenzaldehyde Do. 83 3-methyl-5-pyrazololo Para-nitrosodimethylaniline D0. 84 Hydroxythionaphthene N aphthalene-4-hydroxy-l-aldehyde Brown-orange.

The ds'estufls Nos. 1, s, 14, 20, 26, 27, 29, 39, 41, 56, 57, 67,- 70, and 73 have the following formulas: l No.39

. Y i. o No. 1 {I o-c=co No 41 Ill 1 o I i... NO-o -s =0 mom) A No.56 NH/ l E c-- =on-N(cm I s I E -s No. 57 C;HsN l =NONwHo, Z- =EONB, s/ I. I 1h! No. s7 G G-mom);

, 0 cm I No. 20 l v I cH' I I No.70 e-c=c C -N 0nm o 1 It s l H E 41- mom). No.'2o (cum-N004 -C=CONO e I i i i l i No. 73 C= 0 A} No. 27 (cHorNO-c=c-:":-c=c-c=c- A A i 1& A 1!! What I claim is: 0N I ON 1. A. process for dyeing or coloring cellulose No.29 '(!7=CHO-OH=(E esters or cellulose ethers, consisting in dyeing or coloring the material by means of'a. colored prod a not of the general formula. R1=CHR2 wherein R1 stands for any residue of a compound contain= vii ing a hetero'cyclically bound reactive methylene group, and R2 for any aryl residue.

2. A process for dyeing or coloring cellulose esters or cellulose ethers, consisting in dyeing or coloring the material by means of a colored product which can be obtained by condensing an aromatic aldehyde with compounds containing a heterocyclically bound reactive methylene group.

3. A process for dyeing or coloring cellulose esters or cellulose ethers, consisting in dyeing or coloring the material by means of a colored product which can be obtained by condensing an arcmatic amino aldehyde with compounds containing a heterocyclically bound reactive methylene group.

4. A process for dyeing or coloring cellulose esters or cellulose ethers, consisting in dyeing or coloring the material by means of a colored product which can be obtained by condensing an aromatic para-dialkylamino-aldehyde with compounds containing a heterocyclically bound react-ive methylene group.

5. A process for dyeing or coloring cellulose esters or cellulose ethers, consisting in dyeing or coloring thematerial by means of a colored product which can be obtained by condensing an aromatic para-dialkylamino-aldehyde whose alkyl groups contain not more than two carbon atoms each with compounds containing a heterocyclically bound reactive methylene group.

6. A process for dyeing or coloring cellulose esters or cellulose ethers, consisting in dyeing or coloring the material by means of a colored prod uct which can be obtained by condensing a paradialkylamino-benzaldehyde, whose alkyl groups contain not more than two carbon atoms each with compounds containing a heterocyclically bound reactive methylene group.

7. A process for dyeing or coloring cellulose esters or cellulose ethers, consisting in dyeing or coloring the material by means of a colored product which can be obtained by condensing a paradialkylamino-benza.ldehyde, whose alkyl groups contain not more than two carbon atoms each, with l-phenyl-3-methyl-5-pyrazolone.

8. A process for dyeing or coloring cellulose esters or cellulose ethers, consisting in dyeing or coloring the material by means of a colored product which can be obtained by condensing a paradialkylamino-benzaldehyde, whose alkyl groups contain not more than two carbon atoms each, with 1 -(2'- chloro) -phenyl-3-methyl-5-pyrazolone.

FRANZ ACKERMANN. 

